Chemiluminescence from o-oxalylhydroxyl amine compounds

ABSTRACT

Novel O-oxalylhydroxyl-amine compositions of matter and reactions and to the direct generation of light from chemical energy employing such compositions. By &#39;&#39;&#39;&#39;light&#39;&#39;&#39;&#39; as referred to herein is meant electromagnetic radiation at wavelengths falling between about 350 m Mu and 800 m Mu .

United States Patent 1191 Bollyky et al.

1451 Sept. 30, 1975 CHEMILUMINESCENCE FROM O-OXALYLHYDROXYL AMINECOMPOUNDS [75] Inventors: Laszlo Joseph Bollyky; Robert Henry Whitman,both of Fairtield, Conn.

[73] Assignee: American Cyanamid Company,

Stamford, Conn.

22 Filed: Dec. 18,1969

21 Appl. No.: 886,395

Related U.S. Application Data Continuation-in-part of Ser. No. 547,761,May 5,

1966, abandoned.

52 us. 01. 252/l88.3; 252/186; 252/3012 51 111:.c1. C09K 3/00; c011313/00 [58] Field of Search 252/1883, 186, 301.2

[56] References Cited UNITED STATES PATENTS 3,425,949 2/1969 Rauhut252/1883 Primary Examiner-John D. 'Welsh Attorney, Agent, orFirm-Charles J. Fickey; Gordon L. Hart [57} ABSTRACT 6 Claims, NoDrawings CHEMILUMINESCENCE FROM O-OXALYLHYDROXYL AMINE COMPOUNDS Theinvention herein described was made in the course of or under a contractwith the Department of the Navy.

This application is a continuation-in-part of previously filedapplication Ser. No. 547,761. filed May 5, 1966 now abandoned.

The present invention relates to novel O oxalylhydroxyl-aminecompositions of matter and reactions and to the direct generation oflight from chemical energy employing such compositions. By light asreferred to herein is meant electromagnetic radiation at wavelengthsfalling between about 350 my. and 800 mu.

The art of generating light from chemical energy, i.e.,chemiluminescence, is continually in search of compositions which whenreacted substantially improve the intensity and lifetime of lightemission as contrasted to known chemiluminescent compositions andreactions. Obviously, improved compositions are constantly in demand foruse as signal devices. for area illumination, etc.

It is an object of this invention to obtain a chemiluminescentcompositions and a process employing said composition whereby a highefficiency may be obtained in the conversion of chemical energy intolight.

Another object is to obtain a chemiluminescent com pound which produceslight over an extended period of time.

Another object of this invention is to obtain a chemiluminescentcomposition which attains light of substantially higher intensity thanhas been obtained with former chemiluminescent compositions.

Another object of this invention is to obtain a chemiluminescentcomposition which may be employed to obtain light by a process which ismechanically simple and which is economically inexpensive.

Another object of this invention is to obtain a chemiluminescentreactant which is stable over a long period of time and which may besubsequently reacted to obtain a chemiluminescent light.

Another object of this invention is to obtain a chemiluminescentreactant which when reacted will obtain chemiluminescent light by aprocess which is not hazardous.

The term chemiluminescent reactant, as used herein. means l a mixturewhich will result in a chemiluminescent reaction when reacted with othernecessary reactants in the processes as disclosed herein. or (2) achemiluminescent composition.

The term fluorescent compound". as used herein, means a compound whichfluoresces in a chemilumi nescent reaction. or a compound which producesa fluoreseent compound in a chemiluminescent reaction.

The term chemiluminescent composition, as used herein, means a mixturewhich will result in chemilumineseence.

The term admixing. as used herein, means reacting or sufficientlybringing together component reactants to obtain a chemiluminescentreaction.

The term hydroperoxide compound" as used herein is limited to peroxidecompounds having at least one HOO- group, or a compound which uponreaction produces a compound with such a group.

The term peroxidic groups, as used herein, repre ll sents HOO-, ROO-",or RCOO-,

where R is an organic substituent, such as alkyl, cycloalkyl,a-hydroxyalkyl, substituted alkyl, for example.

The term diluent", as used herein. means a solvent or a vehicle whichwhen employed with a solvent does not cause insolubility.

The term peroxide compound, as used herein. also includes compoundswhich upon reaction produce the peroxide group.

The term oxalyl-type" refers to a compound having at least twoconsecutive (adjacent) carbonyl groups.

The term hydrogen peroxide compound includes l hydrogen peroxide and (2)hydrogen peroxideproducing compounds. I

We have unexpectedly discovered that the objects of this invention areobtained by admixing (I) an oxalyltype O-oxalylhydroxylamine or anothercompound of the typical oxalyl-type Oacylhydroxylamine structure (asdescribed fully below), (2) a hydroperoxidc. (3) a fluorescent compound,and (4) a diluent.

The objects of this invention. are obtained'by employment, with othernecessary chemiluminescent reactants, of an oxalyl-typeO-acylhydroxylamine of the typical formula:

in which B is a polycarbonyl group which is a substituent of each of Aand G, B being of the formula:

where n is an integer of at least one. in which A is a hydroxylaminecompound onto which one of the terminal acyl groups of said B issubstituted onto the hydroxylamine oxygen atom of said A, in which A isa substituted hydroxylaminc compound derived from a hydroxyl amineselected from the group consisting of compounds of the formula:

in which n and n each are integers of atleast one. in which D. D E. andE are each a nitrogen atom. in which R and R are each selected from thegroup consisting of substituted and unsubstituted alkyl. aryl.heteroaryl, acyl and aroyl in which R" and R each are selected from themembers of R and hydrogen. in which R''. R. each are selected from thegroup consisting of diacyl, alkylene. alkylene-diarylene. andalkylenediheteroarylene; and in which said G is selected from the groupconsisting of: l said A; (2) an alcohol (including phenols) of theformula R-O H forming an ester of one of the terminal acyl groups ofsaid B,-in which R is selected from the group consisting of (a)electronegatively substituted saturated alkyl, (b) electronegativelysubstituted aryl, (c) cyclic heteroaryl, (d) heterocyclicalkylaryl, and(e) unsaturated alkyl; and

(3) an electronegatively substituted amine group lsc- N--H. l ly/ and(b) strongly electonegatively N-substituted (substituted ornon-substituted) nitrogen-containingheterocyclic compounds, where the Nis attached directly to thebarbonyl'carbon of the oxalic acid oroxalic-type derivative. typical. N-substitu'ted nitrogen-containingheterocyclic compounds including compounds of the f rmula 4 i where anyone or more of the heterocyclic compounds may include typicalele'ct'ronegative substituents such as above (a thr )t 1gl 1 (c)including halogen. sulfo, oxygen-substituted phosphorous substituent,etc.; where R" is selected from the electronegative group consisting of:1) nitro, (b) oxygenated-sulfur substitucnts such as l] where R and Rare each selected from the group consisting of alkyl. aryl, cyc'loalkyl,heterocyclic. and

' polycyclic substituents, and where R and R"" are each scribes thenumber of oxo groups, onthe i'he teroarw matic ring, I w y I I gSpecific examples of the compounds characterized by A ofthe typicalformula A-B-G; are as follows:

I. A substituted .hydroxylamihe of the typical formula:

: N' o '-H where at least one of R and R is an A. alkyl group: e.g.,decyl-; pentyl-; ethyl-; isopropyl-; eyclohexyl-; etc. or substitutedalkyl groups, by typical substituents such as: i

a. by halogen: e;g., chloromethyl chloropentyl-,

bromobutyl-; v b. by carboxyl groups: e.g.

. boxyethylr; c. by tertiary amino groups: e.g.,methyl(phenylsulfonyl)aminoethyl-,.dimethylarninoethyl; 1 d. byheterocyclic groups: e.g., pyridylethyl-. furylmethyl-,tetrahydrofur-ylpropyl-, -acridinylethyl-; e. by sulfo groupsL-eg,sulfom'ethyl: B. aryl, group: e.g., phenyl-, naphthyl-, or substitutedarylgroups by-typical substituents such as: a. by halogen: e.g.,chlorophenyl-, bromophenyla b. by acyloxy groups: e.g.,benzoyloxyphenyl-; c. by carbonyl groups: e-,g., formylphenylacetylphenyl-; 7 q d. by carboxyl groups: e.g. ,i-carboxyphenyl-; e. byalkoxygroups: e.g., methox yphenyl f. by-amino groups: e.g.,acetylam'inophenyb. diethylaminophenyl-; g. by heterocyclic groups:e.g., pyridylphenyl-,

- tetrahydrofurylpheny-l-;'- h. by. sulfo groups: e.g.,-, sulfophenyl-,I 4- sulfonaphthyl-; v I i. by carboxy groups: e.g.,2-carbobutoxy-3,4,6,- trichlorophcnyl; C; heterocyclic group: e.g.,pyridyl-{furyl acridinyltetrahydrofuryl-, or substituted hteterocyclicgroups by typical substituentsQsuch as:

by alkyl, groups: e.g., methy lpyridyl-; bpby halogen:e.g.,chloropyridyl-; y

. by acyloxy groups: e.g., acetoxypyridyl-; by carbonyl groups: e.g.,forrnylpyridyl-; by carboxyl groups: e.g.r, carboxypyridyl-;

by alkoxy groups: e.g., methoxyfuryl-; by amino groups: e.g.,dirnethylaminotetrahydrofuryl-l h. by sulfo groups: e.g.. sulfofuryl-;i. by hydroxyl groups: e.g., hydroxypyridyl-; D. unsaturated alkyl andcyclic alkyl groups: e.g., vi-

nylallyl-. ethynyL. cyclohexenyl-,- isopropenyl-. II. A substitutedhydroxylamine of the typical formula:

, carboxymethyL, carwhere R is a substituent defined above such as:

alkylene groups? ethylenetrimethylcne 2- oxotrimethylene-,tetramcthylcne-, l-cyanotetramethylene- 2- pentamethylene.

Continued (trichlorophosphoranylidenc sulfumoyl )phenylamine [tris(diphenylamirlo )phosphoranylidencsulfamoyl lmethylamine ammonio)phenyl]amine As stated above G may be a 2 Zhydro-Z oxoheteroaromatic compound.Illustrative examples of this group of compounds are as follows:

1. that contain one oxo substituent as: e.g.,1,2-dihydro-2-oxoquinoline, t l,2-dihydro-2-oxopyridine,l,5-dihydro-5-oxoquinoline, 2,3-dihydro-3- oxoisoquinolinc, etc. i

9,lO-dihydro-9-oxoacridinc (i.c.: acridone); 2. compounds that containmore than one oxo substitu ent as: t e.g., l,2,3,4-tetrahydro2.4-dioxopyridine, l,2,3,4,5,6-hcxahydro-2,4,o-trioxopyridine. l,2,3,4-tetrahydro-2,4-dioxoquinoline4 Other typical 2 Z'hydro-Zoxoheteroaromatic compounds that contain at least one nitrogen and atleast another heteroatom other than nitrogen, include:

1. that contain one oxo substituent as:

e.g., 2,3dihydro-3oxoisothiazole.

- 2,3-dihydro-2-oxooxazole. r 45 2. that contain more than one oxosubstituent e.g., 2,3,4,5-tetrahydro-3,4-dioxoisoxa2ole. Typical 2Z'hydro-z oxohetcroaromatic compounds that contain more than onenitrogen heteroatom include: I

50 1. compounds that contain more than one nitrogen heteroatom butwhich:

a. contain only one oxo substituent e.g..l,2-dihydro-2-oxo-1,3,5-triazine.

l,6-dihydro-6-oxopentazine,

b. contain more than one oxo substituent e.g., hexahydro-2,4,6-trioxo-l,3,5-triazine;

2. compounds that contain more than one nitrogen heteroatom and at leastanother heteroatom other than nitrogen but which: V a. contain only one0x0 substituent e.g., 2,3-dihydro 3-oxofurazan. 4,5-dihydro'5-ox'o-l,2,3,4-oxatriazole,

b. contain more than one oxo substituent e.g.,tetrahydro-2,5-dioxo-1,3,4-oxadiazole, tctrahydro-3,4-dioxofurazan.

Specific examples of the typical formula A B G defined above are asfollows:

and process of this invention may be obtained from any suitable peroxidecompound. For example, the hydroperoxide may be employed as sodiumperoxide. Alternatively, sodium perborate may be placed in aqueous 1 60taxi-nedf Obviously, hydrogen peroxide or its solution may be employed..The peroxide employed may be obtained fromanh ydrous hydrogenper'oxidecompounds 65 of pyrophosphate (sodium pyrophosph'ate peroxide himZ-nxupiper solution whereby a'solution'ofhydrogen peroxideis ob such asperhydrate-of urea (urea'r er'oxide'); perhydrate minmuxulitw w lperhydrate:of'histicline(histidine peroxide), sodium perboratc, and thelike. Still another form in which the H may be provided in thecomposition is that of an anhydrous solution of'H O in a suitablesolvent such as an ether, an ester, an aromatic hydrocarbon, etc. of thetype which would provide a suitable diluent for the composition of thisinvention. Alternatively, the hydroperoxide employed in the compositionor process could be any compound having a hydroperoxidic group, such asa hydroperoxide (ROOH) or a peroxy acid such as t-butyl hydroperoxideand perbenzoic acid. Whenever hydrogen peroxide is contemplated to beemployed, any suitable compound may be substituted which will producehydrogen peroxide.

The hydroperoxide concentration may range from about 15 molar down toabout 10 preferably about 2 molar down to about molar. TheO-acylhydroxylamine of this invention may be added as a solid or inadmixture with a suitable solid peroxide reactant or in a suitablediluent, or alternatively dissolved directly in a solution containingthe peroxide reactant.

Typical diluents within the purview of the instant discovery are thosethat do not readily react with a peroxide such as hydrogen peroxide, andwhich do 'not readily react with an O-acylhydroxylamine.

Although the addition of water is not necessary for the production ofchemiluminescent light in certain embodiments according to the presentinvention, water can serve as the sole diluent or partial diluent. Theterm water, as used herein, includes water-producing compounds such ashydrates. In addition, however, either one or more diluents may beincluded with or in the place of the water, as long as the peroxide employed is at least partially soluble in the diluents(s), such as, forexample, at least one-tenth gram of H 0 per liter of diluent. Thefollowing are illustrative of the additional diluents or solvents whichmay be employed: non-cyclic or cyclic ethers, such as diethyl ether,diamyl ether, diphenyl ether, anisole, tetrahydrofuran, dioxane, andthelike; esters such as ethyl acetate, propyl formate, amyl acetate,dimethyl phthalate, diethyl phthalate, methyl benzoate, and the like;aromatic hydrocarbons, such as benzene, xylene, toluene, and the like.

When water is used as the sole diluent in certain chemiluminescentcompositions, additives can be used optionally to enhance the solubilityof the oxalate and of the fluorescer in this reaction medium. Suchadditives are: ammonium, phosphonium salts, amine oxides and othersurface active agents e.g., tetrabutylammonium perchlorate,tetrabutylammonium salicylate, bis(2- hydroxyethyl) octadecylamineoxide, bis(2- hydroxyethyl) cocoamine oxide, tetrabutylphosphoniumhexafluorophosphate and tetrabutylphosphomium perchlorate.

The fluorescent compounds contemplated herein are numerous; and they maybe defined broadly as those which do not readily react on contact withthe peroxide employed in this invention, such as hydrogen peroxide;likewise, they do not readily react on contact with the ester of oxalicacid. Typical suitable fluorescent com pounds for use in the presentinvention are those which have a spectral emission falling between 330millimicrons and 800 millimicrons and which are at least partiallysoluble in any of the above diluents, if such diluent is employed. Amongthese are the conjugated polycyclic aromatic compounds having at least 3fused rings, such as: anthracene, substituted anthracene,benzanthracene, phenanthrcne, substituted phenanthrene, naphthacene,substituted naphthacene, pentacene, substituted pentacene, and the like.Typical substituents for all of these are'pphcnyl, lower alkyl, chloro,bromo, cyano, alkoxy (C C and other like substituents which do notinterfere with the lightgenerating reaction contemplated herein.

Numerous other fluorescent compounds having the properties givenhereinabove are well known in the art. Many of these are fully describedin Fluorescence and Phosphorescence, by Peter Pringsheim. lntersciencePublishers. Inc. New York, N.Y., 1949. Other fluorescers are describedin The Colour lndex, Second Edition, Volume 2, The American Associationof Textile Chemists and Colorists, 1956, pp. 29072923. While onlytypical fluorescent compounds are listed hereinabove, the person skilledin the art is fully aware of the fact that this invention is not sorestricted and that numerous other fluorescent compounds having similarproperties are contemplated for use herein.

It should be noted, however, that although a fluorescent compound isnecessary to obtain the production of light, the fluorescent compound isnot necessarynto obtain a chemical reaction and chemical energy release.Also, a fluorescent O-aeylhydroxylamine such as phthalimido3,6,8-trisulfo-2-napthyl oxalate does not require a separate fluorescentcompound to obtain light. Thus, a reactant including a fluorescentO-acylhydroxylamine would thereby include at least one flu oreseentcompound. t

It has been found that the molar (molesper liter of diluent)concentrations of the major'components of the novel composition hereindescribed may vary considerably. It is only necessary that components bein sufficient concentration to obtain chemiluminescence. TheOacylhydroxylamine molar concentration normallyis in the range of atleast about 10 to 5 molar, preferably in the range of at least about 10to about 1 molar; the fluorescent compound is present in the range fromabout 10 to 5, preferably to 10 and the water or other diluent must bepresent in a sufficient amount to form at least a partial solution ofthe reactants in' volved in the chemiluminescent reaction. There is noknown maximum limit on the concentration of O-acylhydroxylamine employedin the reaction. The ester may serve as either the sole diluent or apartial diluent.

The ingredients of the composition of this invention, may be admixed ina single stage of admixing or in a sequence of steps of admixing theseparate ingredients. Accordingly, alternative compositions may beprepared which may be stored over a period of time and which may beadmixed with the final ingredient at a time when the chemiluminescentlighting is desired. For example, one such composition would be acomposition which includes an O-acylhydroxylamine and a fluorescentcompound but which does not include a peroxide compound.- Anotheralternative composition would be a composition which includes thefluorescent compound and a peroxide, but which does not include theO-acylhydroxylamine. Another alternative composition would be a solidcomposition which includes a solid Oacylhydroxylamine and a solidhydroperoxide compound, and possibly additionally includes a solidfluorescent compound, but which does not include a diluent. Obviouslythe preferred composition which would be less than all necessarycomponents to produce a chemiluminescent light would be a compositionwhich would be'substantially stable to a practical degree over anextended period of time; otherwise, there would be no real advantage informing a chemiluminescent reactant to be employed in a subsequentchemiluminescent reaction.

The wavelength of the light emitted by chemiluminescence of thecompositions of this invention, i.e., the color of the light emitted,may be varied by the addition of any one or more energy transfer agents(fluorescers) such as the known fluorescent compounds discussed atlength above.

. The'wavelength of the light emitted by'the composition of thisinvention will vary, depending upon the particular fluorescent componentemployed in the reaction.

Although in the process of obtaining chemiluminescent'light according tothis invention, it is normally not necessary to employ a specific orderof sequence of steps'in the adding of the individual ingredients of theinventive chemiluminescentcomposition, it has been found that thefluorescent component preferably should be already in the reactionmixture at the time of addition of the last component necessary to bringabout the chemical-reaction and the concurrent release of chemicalenergy.

Aditionally, it has been found that the superior intensity ofchemiluminescence is obtained when the final mixture producing theluminescence is maintained at a temperatureof between about '40C. and75C., preferably between about C. and 50C.; however, the luminescence ofApplicants process is not limited to thes'e ranges. However, temperatureis not critical.

" Additionally, the composition and the process which obtains preferredoptimum chemiluminescent light intensity employs a base in an amountsufficient to produce a basic'pH. However, the preferred extendedlifetime is obtained under aboutneutral conditions. Any suitable basewhich does not interfere with the chemiluminescent composition andprocess of this invention may be employed.

A'wide variety of organic and inorganic bases is contemplated, typicalbases being: sodium hydroxide, pota'ssium hydroxide, potassium tertiarybutoxide, sodium ethoxide, sodium methoxide, ammonium hydroxide,tetrabutyl ammonium hydroxide, and triphenyl methide; Lewis bases,including pyridine, triethylamine, quinoline, and the like. Weak basesincluding sodium salicylate, tetrabutyl-ammonium salicylate and thosethat are described indetail in the copending commonly assignedapplication Ser. No. 813846, filed on4/7/69. "The composition and theprocess which obtains chemiluminescent light may optionally employ anacid in an amount sufficient to produce an acidic pH. However, thepresence of acid is not essential to obtain chemiluminescence.

The lifetime and the intensity of the chemiluminescent light can beregulated by the use of certain regulators such as: l

' 1. By the addition of base to the chemiluminescent composition. Boththe strength and the concentration of the base are critical for purposesof regula tion.

2. By the variation of hydroperoxide. Both the type and theconcentration ofhydroperoxide are critical for the purposes ofregulation.

3. By the addition of water.

4. By the addition of a catalyst which changes the rate of reaction ofhydroperoxide with the O-acylhydroxylamine. Catalysts which accomplishthat objective include those described in M. L. Bender, Chem. Revs, Vol60, p. 53 (1960).

The following examples are intended to illustrate the present inventionand are in no way intended to limit the invention except as limited inthe appended claims.

EXAMPLE 1 Preparation of Diphthalimido Oxalate (i.c., anacylhydroxylamine) 1.63 g (0.01 mole) N-hydroxyphthalimide is dissolvedin ml freshly distilled 1,2-dimethoxyethane. To the rapidly stirredsolution 0.43 ml (0.005 mole) oxalyl chloride and 1.4 ml (0.01 mole)triethylamine is added at 25C. After 1 hour stirring the mixture isevaporated to dryness under vacuum and the solid residue is digested 3times with 30 ml portions of chloroform to obtain the product, whitecrystals, m.p. 2334C. .in 42% yield.

Anal. calcd. for C I-1 0 C, 56.85; H, 2.12; N, 7.37. Found: C, 56.10; H,2.00, N, 7.45.

EXAMPLE II The tests of Table l were carried out as follows:

A. Approximately 3-5 mg of the compound of Example l to be tested isadded to a 5 ml solution of about 1 mg 9,10-diphenylanthracene (DPA) and0.2 ml anhydrous H 0 in anhydrous 1,2- dimethoxyethane maintained at25C.

B. Approximately 3-5 mg of the compound of Example I to be tested isadded to a 5 ml slurry of 1 mg DPA, 0.2 g KOl-l (l pellet) and 0.2 mlanhydrous H 0 in anhydrous 1,2-dimethoxyethane maintained at 25C.

C. Part C is conducted the same as test A except that approximately 0.1ml water is added prior to the addition of the compound being tested.

D. Approximately 3-5 mg of the oxalate compound of Example I to betested is added to a 5 ml solution of 1 mg DPA and 0.2 ml CH SO H in1,2- dimethoxyethane containing 5% water and maintained at 25C. About0.2 ml 98% H 0 is added immediately.

Qualitative intensities are based on the oxalyl chlo ride, hydrogenperoxide reaction taken as strong(S). Other designations are M medium; Wweak; VW very weak, barely visible.

The compound is subjected to qualitative chemiluminescent tests as shownin Table I.

TABLE I Tests" Oacylhydroxyl- A B C D amine Anhyd.H O- H. .O KOH H O, HO H O H O N-OC S (long) S (fast) MS (long) W (long) EXAMPLE llI EXAMPLEV Employing the diphthalamido oxalate of Example I, tests A through Eare conducted to determine the lifetime, the quantum yield and theradiation capacity employing dimethyl phthalate solvent, and varyingamounts of the oxalate and the hydrogen peroxide. As a fluorescer,9,10-diphenylanthracene is employed. All measurements are carried out atabout 25C. The lifetime is expressed in terms of (t I the time re quiredfor the light intensity to decrease to one quarter of its minimum value.For'Part D, 0.015 mole l of water is added to the'reaction. For Part E,8.3 X 10" mole 1" of triethylamine is added to the reaction.

For Parts F and G the procedure is the same as for the above Examples Athrough C, except for employing propylene carbonate as the solvent, andvarying the relative quantities of reactants.

EXAMPLE VI Preparation of dimaleimido oxalate is carried out accordingto the procedure shown in Example [except N-hydroxy-maleimide is used inthe place of N-hydroxy phthalimide.

EXAMPLE VII The concentrations of the oxalate and hydrogen per-Preparanon of d1p1per1d1no oxalate. oxide are shown in Table II below.

C|-1 CH 0 Quantitative Measurements of the Chemiluminescence carried outin the two different solvents are shown in /N 0 C Table II. c11 -c1-1 2TABLE II Chemiluminescence Quantum Yield and Radiation Capacity ofDiphthalimido Oxalate O-oxalyl- Example 111 hydroxylamine H2O2 t, 1Quantum Yield Radiation Capacity Part (mole 1) (mole l) (min) (einsteinmole X 10 (einstein 1" X 10) A 0.001 0.024 94.0 8.7 0.9 B 0.010 0.0024307.0 2.3 2.3 C 0.010 0.0090 269.0 1.9 1.9 D 0.010 0.0090 169.0 2.7 2.7E 0.010 0.0090 184.0 4.3 4.3 F 0.0010 0.034 07 2.64 0.26 G 0.0100 0.03410.1 1.41 1.41

EXAMPLE IV is carried out according to the procedure shown in Ex-Diphthalimido oxalate is tested for chemiluminescence in a reaction withhydroperoxides other than hydrogen peroxide. The tests carried out areas follows:

A. Approximately, 3 mg diphthalimido oxalate is added to a 5 ml solutionof 1 mg 9,10- diphenylanthracene (DPA) and 25 mg 4- nitroperoxybenzoicacid in 1,2-dimethoxyethane (DME) maintained at about 25C. Weakchemiluminescence is observed.

B. Test is similar to test A except 0.2 g KOl-I is also added. Mediumweak chemiluminescence is observed.

C. Test is similar to test A except 0.1 ml water is also added. Nosubstantial chemiluminescence is observed.

D. Test is similar to test A except 0.1 ml methanesulfonic acid is alsoadded. No substantial chemiluminescence is observed.

ample 1 except Nhydroxy p iperidine is used in the place of N-hydroxyphthalimide.

EXAMPLE VIII The preparation of disuceinimido oxalate: to a mixture of11.5 g (0.1 mole) N-hydroxy succinimide 200 ml benzene and 200 mlanhydrous ether. 13.95 ml (0.1 mole) triethylamine and 4.26 ml (0.05mole) oxalyl chloride were added to obtain a brown slurry which wasdiluted with 500 ml benzene, stirred for 90 minutes and filtered toobtain a brown. solid. This solid was reslurried with ml chloroformfiltered and washed with two 30 ml portions of chloroform to obtain alight brown solid which was reslurried again with 800 ml ethyl acetatefiltered and washed with two portions of 40 ml acetone and dried toobtain approximately 4.5 g 16% of theory) light brown hydroscopic solidproduct mp. 176C (decomposes).

19 Anal. calcd. for c,.,H,,o,N c, 42.26; H,2.84, N, 9.86. Found: c,42.37: H, 3.16, N,- 9.78.

EXAMPLE IX Qualitative chemiluminescence tests of disuccinimido oxalatein tetrahydrofuran solvent: A very bright green chemiluminescent lightemission is obtained when approxmately 3 mg disuccinimido oxalate isadded to a 2 ml solution of 0.3 molar hydrogen peroxide and 0.001 molar9,10-bis(phenylcthnyl) anthracene in tetrahydrofuran.

EXAMPLE x Qualitative chemiluminescence tests of disuccinimido oxalatein 3-methyl-3-pentanol solvent: Three experiments were carried out asdescribed in Example IX except a different fluorescer was "used in eachcase, 9,10-b is(phenylethyn yl) anthracene, i N- methy lac ri di uii'nchloride and sodium fluorcscein. Moderately weak light emissions wereobtained in the presence of all three fluorescers in 3-methyl-3-pentanola tertiary alcohol solvent.

mately 0.5 g tetrabutylammonium perchlorate is added to the solution.

It is within the scope of this invention to make such modifications ofthe compositions and processes disclosed herein as would be obvious to aperson of ordinary skill in this art, and it is to be understood thatthe tests of disucexamples illustrating this invention are intended tolimit the invention only insofar as is'stated in the specification andas the following claims are limited. Also, it within the scope of thisinvention to form an apparatus or article such as a container which, forexample may be either (1) a substantially insoluble or alternatively (2)a dissolvable capsule in which the reactant or composition of thisinvention is substantially enclosed for subsequent reaction with otheringredients necessary to produce chemiluminescent light.

We claim:

1. A composition intended to be reacted with a hydroperoxide to producechemiluminescent light, said composition containing the ingredients (1)a compound of the formula where B is n is an integer at least one, Aahydroxylamine group, and G is selected from the group consisting ofhydroxylamine. oxime, alcohol and aminegroups, (2) an organicfluorescent compound and (3) a solvent for said ingredients. I v

"2. A composition according .to claim 1 in which the compound of theformula defined is selected from diphthalimido oxalate disuccinimidooxalate and the composition furthercomprises hydrogen peroxide.-

3; A composition according to claim 1 where said solvent is water and anoptional tetraalkylamm onium salt additive is present. I g

4. A composition according to claim 3 where said'fluorescer is selectedfrom the group consisting of sodium fluorercein, N-methylacridiuimsalts, 9,l0-bis(carbomethyoxyethynyl) anthracene.

5. A composition according to claim -1 further comprising hydrogenperoxide or a hydrogen peroxide precursor.

6. Acomposition according to claim3 further comprising an alkali metalperborate.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORECTION Patent No.3,9o9,nn0 Dated September 30, 1975 Inventor(s) LASZLO JOSEPH BOLLYKY andROBERT HENRY WHITMAN It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

Column 20, line 15, after the word "formula" insert A-B-G- Column 20,line 29, after the word oxalate", first occurrence,

insert and Signed and Scaled this Attest:

RUTH C. MASON C. MARSHALL DANN Atresring Officer Commissioner oj'larenlsand Trademarks UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION pPatent No. 3,909,L[ L O Dated September 30, 1975 Inventor(s) LASZLOJOSEPH BOLLYKY and ROBERT HENRY WHITMAN It is certified that errorappears in the above-identified patent and that said Letters Patent arehereby corrected as shown below:

Column 20, line 15, after the word "formula" insert A B G Column 20,line 29, after the word "oxalate", first occurrence,

insert and Signed and Scaled this A Thirty-first Day of August'1976Arrest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner vj'Parentsand Trademarks UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTIONPatent No. '3,9O9,L|J LO Dated September 30, 1975 Inventor(s) LASZLOJOSEPH BOLLYKY and ROBERT HENRY WHITMAN It is certified that errorappears in the above-identified patent and that said Letters Patent arehereby corrected as shown below:

Column 20, line 15, after the word "formula" insert --AB-G- Column 2O,line 29, after the word "oxalate", first occurrence,

insert and Signed and Sealed this Arrest.

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner nfPatenlsand Trademarks

1. A COMPOSITION INTENDED TO BE REACTED WITH HYDROPEROXIDE TO PRODUCECHEMILUMINESCENT LIGHT, SAID COMPOSITION CONTAINING THE INGREDIENTS (1)A COMPOUND OF THE FORMULA WHERE B US
 2. A COMPOSITION ACCORDING TO CLAIM1, IN WHICH THE COMPOUND OF THE FORMULA DEFINED IS SELECTED FROMDIPHTHALIMIDO OXATATE DISUCCININIMIDE OXALATE AND THE COMPOSITIONFURTHER COMPRISES HYDROGEN PEROXIDE.
 3. A COMPOSITION ACCORDING TO CLAIM1 WHERE SAID SOLVENT IS WATER AND AN OPTIONAL TETRAALKYLAMMONIUM SALTADDITIVE IS PRESENT.
 4. A composition according to claim 3 where saidfluorescer is selected from the group consisting of sodium fluorercein,N-methylacridiuim salts, 9,10-bis(carbomethyoxyethynyl) anthracene.
 5. Acomposition according to claim 1 further comprising hydrogen peroxide ora hydrogen peroxide precursor.
 6. A composition according to claim 3further comprising an alkali metal perborate.